JP2023124039A - heavy metal adsorbent - Google Patents
heavy metal adsorbent Download PDFInfo
- Publication number
- JP2023124039A JP2023124039A JP2022027587A JP2022027587A JP2023124039A JP 2023124039 A JP2023124039 A JP 2023124039A JP 2022027587 A JP2022027587 A JP 2022027587A JP 2022027587 A JP2022027587 A JP 2022027587A JP 2023124039 A JP2023124039 A JP 2023124039A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- zeolite
- adsorbent
- type
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 63
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000010457 zeolite Substances 0.000 claims abstract description 63
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 58
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010828 elution Methods 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229940126062 Compound A Drugs 0.000 claims description 46
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000008399 tap water Substances 0.000 description 8
- 235000020679 tap water Nutrition 0.000 description 8
- 238000000691 measurement method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- -1 analcyme Inorganic materials 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910002039 SYLYSIA SY350 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
Description
本発明は重金属吸着剤に関する。 The present invention relates to heavy metal adsorbents.
水道水中の鉛濃度は、鉛は健康への影響が懸念されるため、我が国における水質基準の一つになっている。水道水に含まれる鉛は、１９００年代前半まで水道管として使用されていた鉛管に由来するとされている。
水に含まれる鉛等の重金属を吸着できるゼオライト（アルミノケイ酸塩系無機イオン交換体）は、浄水器用の吸着剤として使用されている（特許文献１）。
一方、ゼオライトには、水中に長期間浸漬させたときに、構成元素であるアルミニウムが浄化水中へ溶出するという問題がある。これを解決する手段として、吸着剤におけるゼオライト含有粒子の体積粒度分布を制御する技術が知られている（特許文献２及び３）。
The concentration of lead in tap water is one of the water quality standards in Japan because of concerns about the health effects of lead. Lead contained in tap water is said to be derived from lead pipes that were used as water pipes until the early 1900s.
Zeolites (aluminosilicate-based inorganic ion exchangers) capable of adsorbing heavy metals such as lead contained in water are used as adsorbents for water purifiers (Patent Document 1).
On the other hand, zeolite has a problem that when it is immersed in water for a long period of time, its constituent element aluminum is eluted into the purified water. Techniques for controlling the volume particle size distribution of zeolite-containing particles in adsorbents are known as means for solving this problem (Patent Documents 2 and 3).
ゼオライトを重金属吸着剤として使用する際のアルミニウムの溶出を抑制する新しい手段を提供することを課題として設定した。 The purpose of this study was to provide a new means of suppressing the elution of aluminum when zeolite is used as a heavy metal adsorbent.
前記の課題を鋭意検討した結果、本発明者は、特定金属種の含水酸化物又は水酸化物をゼオライトと組合わせると、ゼオライトからのアルミニウムの溶出を抑制できることを見出した。本発明は、この知見に基づいてなされたものである。 As a result of intensive studies on the above problems, the present inventors have found that the elution of aluminum from zeolite can be suppressed by combining a hydrous oxide or hydroxide of a specific metal species with zeolite. The present invention has been made based on this finding.
すなわち、本発明は、以下の〔１〕～〔１１〕に関するものである。
〔１〕Ｓｉ、Ｔｉ、Ｚｒ、Ｃｅ又はＬａの含水酸化物又は水酸化物である化合物Ａとゼオライトとを含む、重金属吸着剤。
〔２〕化合物ＡのＢＥＴ比表面積が５０ｍ2／ｇ以上である、前記〔１〕に記載の吸着剤。
〔３〕化合物Ａの１質量％水分散液のｐＨが１０以下である、前記〔１〕又は〔２〕に記載の吸着剤。
〔４〕化合物Ａとゼオライトとの合計質量に対して、３質量％以上の化合物Ａを含む、前記〔１〕～〔３〕のいずれか一項に記載の吸着剤。
〔５〕ゼオライトのメジアン径が１０μｍ以上である、前記〔１〕～〔４〕のいずれか一項に記載の吸着剤。
〔６〕ゼオライトが、Ａ型、Ｘ型、Ｙ型又はＰ型のゼオライトである、前記〔１〕～〔５〕のいずれか一項に記載の吸着剤。
〔７〕アルミニウムの溶出量が５ｐｐｍ以下である、前記〔１〕～〔６〕のいずれか一項に記載の吸着剤。
〔８〕鉛吸着剤である、前記〔１〕～〔７〕のいずれか一項に記載の吸着剤。
〔９〕浄水器用の吸着剤である、前記〔１〕～〔８〕のいずれか一項に記載の吸着剤。
〔１０〕前記〔１〕～〔９〕のいずれか一項に記載の吸着剤を含む、浄水器。
〔１１〕ゼオライトを含む重金属吸着剤からのアルミニウムの溶出を抑制する方法であって、
Ｓｉ、Ｔｉ、Ｚｒ、Ｃｅ又はＬａの含水酸化物又は水酸化物である化合物Ａを前記吸着剤へ添加する工程を含む方法。
That is, the present invention relates to the following [1] to [11].
[1] A heavy metal adsorbent containing compound A, which is a hydrous oxide or hydroxide of Si, Ti, Zr, Ce or La, and zeolite.
[2] The adsorbent according to [1] above, wherein the BET specific surface area of compound A is 50 m 2 /g or more.
[3] The adsorbent according to [1] or [2] above, wherein the 1% by mass aqueous dispersion of compound A has a pH of 10 or less.
[4] The adsorbent according to any one of [1] to [3], which contains 3% by mass or more of compound A with respect to the total mass of compound A and zeolite.
[5] The adsorbent according to any one of [1] to [4], wherein the zeolite has a median diameter of 10 μm or more.
[6] The adsorbent according to any one of [1] to [5], wherein the zeolite is A-type, X-type, Y-type or P-type zeolite.
[7] The adsorbent according to any one of [1] to [6] above, wherein the amount of eluted aluminum is 5 ppm or less.
[8] The adsorbent according to any one of [1] to [7], which is a lead adsorbent.
[9] The adsorbent according to any one of [1] to [8], which is an adsorbent for water purifiers.
[10] A water purifier comprising the adsorbent according to any one of [1] to [9].
[11] A method for suppressing elution of aluminum from a heavy metal adsorbent containing zeolite,
A method comprising the step of adding Compound A, which is a hydrous oxide or hydroxide of Si, Ti, Zr, Ce or La, to said adsorbent.
後述の実施例で示されるように、本発明に従うとゼオライトからのアルミニウムの溶出を抑制できる。したがって、本発明は、従来製品にはない商品価値を有する重金属吸着剤やこれを利用した浄水器を提供できる。 As shown in the examples below, according to the present invention, elution of aluminum from zeolite can be suppressed. Therefore, the present invention can provide a heavy metal adsorbent having commercial value not found in conventional products and a water purifier using the same.
本発明の重金属吸着剤（以下、「吸着剤」ともいう）は、後述する化合物Ａとゼオライトとを必須成分として含有する。 The heavy metal adsorbent (hereinafter also referred to as "adsorbent") of the present invention contains compound A and zeolite, which will be described later, as essential components.
〔化合物Ａ〕
化合物Ａは、ゼオライトからのアルミニウムの溶出を抑制するために用いる。
化合物Ａは、Ｓｉ、Ｔｉ、Ｚｒ、Ｃｅ又はＬａの含水酸化物又は水酸化物である。尚、含水酸化物は水和酸化物とも呼ばれるが、本明細書では含水酸化物として記載する。
化合物Ａは、Ｓｉ、Ｔｉ、Ｚｒ、Ｃｅ及びＬａの２種以上を含んでいてもよい。
[Compound A]
Compound A is used to suppress the elution of aluminum from zeolite.
Compound A is a hydrous oxide or hydroxide of Si, Ti, Zr, Ce or La. Although the hydrous oxide is also called a hydrated oxide, it is described as a hydrous oxide in this specification.
Compound A may contain two or more of Si, Ti, Zr, Ce and La.
化合物Ａの具体例としては、以下のA1～A14が挙げられる。 Specific examples of compound A include the following A1 to A14.
これらのなかでは、Ｔｉ、Ｚｒ又はＣｅの含水酸化物又は水酸化物が好ましく、メタチタン酸が更に好ましい。 Among these, hydrous oxides or hydroxides of Ti, Zr or Ce are preferred, and metatitanic acid is more preferred.
化合物ＡのＢＥＴ比表面積は、好ましくは５０ｍ2／ｇ以上、より好ましくは１００ｍ2／ｇ以上、特に好ましくは２００ｍ2／ｇ以上である。ＢＥＴ比表面積が５０ｍ2／ｇ以上であるとゼオライトからのアルミニウムの溶出を更に抑制することができる。
ＢＥＴ比表面積は、以下の方法に従い測定できる。
The BET specific surface area of compound A is preferably 50 m 2 /g or more, more preferably 100 m 2 /g or more, and particularly preferably 200 m 2 /g or more. When the BET specific surface area is 50 m 2 /g or more, the elution of aluminum from the zeolite can be further suppressed.
The BET specific surface area can be measured according to the following method.
［化合物ＡのＢＥＴ比表面積の測定法］
全自動ガス吸着量測定装置（カンタクローム・インスツルメンツ社製 AutosorbiQ）を用いて測定する。詳細には、アルゴン吸着法（８７．４５Ｋ）にて測定を行い、ＢＥＴ多点法による解析で比表面積を求める。また試料の前処理として２００℃で６時間の真空脱気を行う。
[Measurement method of BET specific surface area of compound A]
It is measured using a fully automatic gas adsorption measuring device (AutosorbiQ manufactured by Quantachrome Instruments). Specifically, measurement is performed by the argon adsorption method (87.45K), and the specific surface area is determined by analysis using the BET multipoint method. As a pretreatment of the sample, vacuum deaeration is performed at 200° C. for 6 hours.
化合物Ａの１質量％水分散液のｐＨは、好ましくは１０以下である。
前記の（A1）～（A13）のうち、１質量％水分散液のｐＨが１０以下であるものの例としては、前述のＡ５（ｐＨ：３．３）、Ａ７（ｐＨ：４．５）や、Ａ３（ｐＨ：７．５）などが挙げられる。
化合物ＡのｐＨは以下の方法に従い測定できる。
The pH of the 1% by mass aqueous dispersion of compound A is preferably 10 or less.
Among the above (A1) to (A13), examples of those in which the pH of the 1% by mass aqueous dispersion is 10 or less include the above-mentioned A5 (pH: 3.3), A7 (pH: 4.5), , A3 (pH: 7.5) and the like.
The pH of compound A can be measured according to the following method.
［化合物ＡのｐＨの測定法］
１ｇの化合物Ａを９９ｇのイオン交換水（２５℃）に添加し、５分間攪拌して水分散液（スラリー）を作成する。水分散液のｐＨを、ガラス電極ｐＨメータ（例えば、堀場製作所 Ｆ－５２）で測定する。
[Method for measuring pH of compound A]
1 g of Compound A is added to 99 g of ion-exchanged water (25° C.) and stirred for 5 minutes to prepare an aqueous dispersion (slurry). The pH of the aqueous dispersion is measured with a glass electrode pH meter (eg Horiba F-52).
化合物Ａは公知の物質であり、市場で容易に入手可能であるか、又は調製可能である。
メタチタン酸の市販品としては、堺化学工業(株)製の「ＳＴ－Ｃ」が挙げられる。
水酸化ジルコニウムの市販品としては、第一稀元素工業(株)製の「Ｒ水酸化ジルコニウム」が挙げられる。
含水酸化ケイ素の市販品としては、富士シリシア化学(株)製の「サイリシア」が挙げられる。
Compound A is a known substance and is readily commercially available or can be prepared.
Commercial products of metatitanic acid include “ST-C” manufactured by Sakai Chemical Industry Co., Ltd.
Commercial products of zirconium hydroxide include "R zirconium hydroxide" manufactured by Daiichi Kigenso Kogyo Co., Ltd.
Commercial products of hydrous silicon oxide include “Sylysia” manufactured by Fuji Silysia Chemical Co., Ltd.
Ｔｉ元素を含む化合物Ａは、例えば、以下の方法に従い調製できる。
Ｔｉの水溶性金属塩（例えば、硫酸チタニル）を水に溶解して水溶液を得る。攪拌下、アルカリ（例えば、水酸化ナトリウム）を滴下して前記水溶液のｐＨを上昇させて、沈殿物を得る。沈殿物を熟成（例えば、５～１００℃で１～２４時間）した後、固液分離、水洗及び乾燥（例えば、５０～２００℃で１～１００時間）に供して、化合物Ａを得る。
化合物ＡのＢＥＴ比表面積の制御は、沈殿物生成に用いるアルカリの種類及びｐＨ、熟成温度や乾燥温度を変更することで実施できる。
乾燥温度を２００℃以下にすると、化合物Ａが脱水縮合を起こして金属酸化物へ変化することを抑制できるので好ましい。
Compound A containing Ti element can be prepared, for example, according to the following method.
A water-soluble metal salt of Ti (eg, titanyl sulfate) is dissolved in water to obtain an aqueous solution. Under stirring, an alkali (for example, sodium hydroxide) is added dropwise to raise the pH of the aqueous solution to obtain a precipitate. After aging the precipitate (for example, at 5-100° C. for 1-24 hours), it is subjected to solid-liquid separation, washing with water and drying (for example, 50-200° C. for 1-100 hours) to obtain compound A.
The BET specific surface area of compound A can be controlled by changing the type and pH of the alkali used for forming the precipitate, the aging temperature, and the drying temperature.
A drying temperature of 200° C. or less is preferable because dehydration condensation of the compound A and conversion to a metal oxide can be suppressed.
Ｓｉ元素を含む化合物Ａは、ケイ酸ソーダ溶液へ酸（例えば、硫酸）を滴下することで調製できる。 Compound A containing Si element can be prepared by dropping an acid (for example, sulfuric acid) into a sodium silicate solution.
化合物Ａは単一種類を使用してもよく、複数種類を併用してもよい。 A single type of compound A may be used, or a plurality of types may be used in combination.
化合物Ａの含量は、化合物Ａとゼオライトとの合計質量に対して、好ましくは３質量％以上、より好ましくは１０～５０質量％、特に好ましくは２０～４０質量％である。含量が３質量％以上であると、より高いアルミニウム溶出抑制効果を得ることができる。 The content of compound A is preferably 3% by mass or more, more preferably 10 to 50% by mass, particularly preferably 20 to 40% by mass, based on the total mass of compound A and zeolite. When the content is 3% by mass or more, a higher aluminum elution inhibitory effect can be obtained.
〔ゼオライト（アルミノケイ酸塩）〕
本発明では、重金属を吸着するゼオライトを特に制限なく使用できる。
ゼオライトは、合成ゼオライト及び天然ゼオライトのいずれでもよいが、合成ゼオライトが好ましい。
合成ゼオライトの例としては、Ａ型ゼオライト、Ｘ型ゼオライト、Ｙ型ゼオライト、Ｐ型ゼオライト、Ｔ型ゼオライト、Ｌ型ゼオライトや、β型ゼオライト等が挙げられる。なかでもＡ型、Ｘ型、Ｙ型又はＰ型のゼオライトが好ましい。
天然ゼオライトの例としては、ソーダライト、モルデナイト、アナルサイム、クリノプチロライト、チャバサイトや、エリオナイト等が挙げられる。
[Zeolite (aluminosilicate)]
In the present invention, any zeolite that adsorbs heavy metals can be used without particular limitation.
Zeolite may be either synthetic zeolite or natural zeolite, but synthetic zeolite is preferred.
Examples of synthetic zeolites include A-type zeolite, X-type zeolite, Y-type zeolite, P-type zeolite, T-type zeolite, L-type zeolite, and β-type zeolite. Among them, A-type, X-type, Y-type or P-type zeolites are preferred.
Examples of natural zeolites include sodalite, mordenite, analcyme, clinoptilolite, chabasite, and erionite.
ゼオライトのメジアン径は、好ましくは１０μｍ以上、より好ましくは１０～１０００μｍ、特に好ましくは２０～５０μｍである。メジアン径が１０μｍ以上であると、浄水器フィルターからの吸着剤の流出や前記フィルターの目詰まりを軽減できる。
メジアン径は、レーザー回折・散乱式粒度分布測定法に従い測定できる。
The median diameter of zeolite is preferably 10 μm or more, more preferably 10 to 1000 μm, particularly preferably 20 to 50 μm. When the median diameter is 10 μm or more, it is possible to reduce the outflow of the adsorbent from the water purifier filter and the clogging of the filter.
The median diameter can be measured according to a laser diffraction/scattering particle size distribution measurement method.
ゼオライトは公知物質であり、市場で容易に入手可能であるか、又は調製可能である。市販品としては、株式会社シナネンゼオミック製の「ゼオミック」が挙げられる。
ゼオライトは、単一種類を使用してもよく、複数種類を併用してもよい。
Zeolites are known substances and are readily commercially available or can be prepared. Commercially available products include “Zeomic” manufactured by Sinanen Zeomic Co., Ltd.
A single type of zeolite may be used, or a plurality of types may be used in combination.
〔任意成分〕
本発明の吸着剤は、その効果を損なわない範囲で、活性炭等の任意成分と組み合わせてして使用することができる。
〔活性炭〕
活性炭は、水中に含まれる有害性有機化合物（例えばトリハロメタンやホルムアルデヒド）や、塩素臭やカビ臭を除去するために配合する。
活性炭の形状は、粉末状、粒子状、繊維状の何れでもよい。
活性炭は公知物質であり、市場で容易に入手可能であるか、又は調製可能である。
活性炭は単一種類を使用してもよく、複数種類を併用してもよい。
活性炭の含量は、配合目的を達成できる量である限り特に限定されないが、重金属吸着剤の総質量に対して、好ましくは１００～２０００質量％、更に好ましくは５００～１５００質量％である。
[Optional component]
The adsorbent of the present invention can be used in combination with optional components such as activated carbon within the range that does not impair its effect.
[Activated carbon]
Activated carbon is blended to remove harmful organic compounds (such as trihalomethane and formaldehyde) contained in water, as well as chlorine and mold odors.
The activated carbon may be in the form of powder, particles, or fibers.
Activated carbon is a known substance and is readily available commercially or can be prepared.
A single type of activated carbon may be used, or a plurality of types may be used in combination.
The content of activated carbon is not particularly limited as long as the purpose of blending can be achieved.
〔アルミニウムの溶出量〕
化合物Ａを含む吸着剤では、ゼオライトからのアルミニウムの溶出が抑制されている。以下に示す測定法によるアルミニウムの溶出量は、好ましくは５ｐｐｍ以下、より好ましくは２ｐｐｍ以下、特に好ましくは１ｐｐｍ以下である。
[Elution amount of aluminum]
The adsorbent containing compound A suppresses the elution of aluminum from the zeolite. The elution amount of aluminum measured by the following measurement method is preferably 5 ppm or less, more preferably 2 ppm or less, and particularly preferably 1 ppm or less.
［アルミニウム溶出量の測定法］
模擬水道水（JIS S3200-7に規定される浸出液：pH7.0±0.1、硬度45±5mg/L、アルカリ度35±5mg/L、残留塩素0.3mg±0.1mg/L）へ吸着剤を添加して混合物を調製する（添加量：吸着剤に含まれるゼオライトの量が、模擬水道水の質量に対して１質量％となる量）。
混合物を、恒温振とう培養器（例えば、タイテック株式会社製 バイオシェーカー（登録商標））を用いて２５℃、１７０ｒｐｍで２４時間攪拌する。
攪拌後の混合物を、メンブランフィルター（孔径：０．４５μｍ）を用いた固液分離に供する。
分離した液体中のアルミニウム量を原子吸光光度計で測定し、測定値を溶出量とする。
[Measurement method of aluminum elution amount]
Adsorbent is added to simulated tap water (leaching solution specified in JIS S3200-7: pH7.0±0.1, hardness 45±5mg/L, alkalinity 35±5mg/L, residual chlorine 0.3mg±0.1mg/L) to prepare a mixture (addition amount: the amount of zeolite contained in the adsorbent becomes 1% by mass with respect to the mass of simulated tap water).
The mixture is stirred at 25° C. and 170 rpm for 24 hours using a constant temperature shaking incubator (for example, Bioshaker (registered trademark) manufactured by Taitec Co., Ltd.).
The stirred mixture is subjected to solid-liquid separation using a membrane filter (pore size: 0.45 μm).
The amount of aluminum in the separated liquid is measured with an atomic absorption spectrophotometer, and the measured value is defined as the amount of elution.
〔吸着剤の製法〕
吸着剤は、例えば、所定量のゼオライトと化合物Ａとを粉末状態（例えば、粒子径：１００μｍ以下の粉末）で混合機へ投入し、均一になるまで混合（例えば、数分から数時間）することで製造できる。
混合機は特に限定されないが、工業的にはロッキングミキサー、リボンミキサーや、ヘンシェルミキサー等を用いることができる。
前記の製法とは別に、吸着剤は、ゼオライトと化合物Ａとを水へ投入し、プロペラ攪拌機等で攪拌して両成分が均一に分散したスラリーを作成し、これを固液分離及び乾燥に供することでも製造できる。
[Manufacturing method of adsorbent]
For the adsorbent, for example, a predetermined amount of zeolite and compound A in a powder state (e.g., powder with a particle size of 100 μm or less) are put into a mixer and mixed until uniform (for example, from several minutes to several hours). can be manufactured in
The mixer is not particularly limited, but industrially, a rocking mixer, a ribbon mixer, a Henschel mixer, or the like can be used.
Separately from the above manufacturing method, the adsorbent is prepared by adding zeolite and compound A to water, stirring with a propeller stirrer or the like to prepare a slurry in which both components are uniformly dispersed, and subjecting this to solid-liquid separation and drying. It can also be manufactured by
本発明の吸着剤と活性炭とを組み合わせてなる浄水器用活性炭フィルター（カーボンブロック等）は、例えば、活性炭と吸着剤、又は活性炭と化合物Ａとゼオライトにバインダー（ポリエチレン粉末、フィブリル化繊維等）を所定量で混合した後、成型工程に供することで製造できる。 Activated carbon filters for water purifiers (carbon blocks, etc.), which are obtained by combining the adsorbent and activated carbon of the present invention, can be obtained, for example, by adding a binder (polyethylene powder, fibrillated fiber, etc.) to activated carbon and adsorbent, or activated carbon, compound A, and zeolite. It can be produced by mixing a fixed amount and then subjecting it to a molding process.
〔吸着対象となる重金属〕
吸着する重金属の種類は特に制限されないが、ゼオライトの種類に基づいて適宜選択してもよい。重金属の例としては鉛、カドミウムや亜鉛が挙げられる。Ａ型、Ｘ型、Ｙ型又はＰ型のゼオライトは、鉛、カドミウム及び亜鉛の除去に適しているので好ましい。本発明は、鉛の除去に特に適している。
[Heavy metals to be adsorbed]
The type of heavy metal to be adsorbed is not particularly limited, but may be appropriately selected based on the type of zeolite. Examples of heavy metals include lead, cadmium and zinc. Zeolites of type A, X, Y or P are preferred as they are suitable for the removal of lead, cadmium and zinc. The present invention is particularly suitable for lead removal.
〔吸着剤の用途〕
吸着剤は、水（特に水道水）から重金属を除去するために使用できる。
なかでも、水道水から鉛を除去する浄水器用の吸着剤として好適に使用できる。
[Use of adsorbent]
Adsorbents can be used to remove heavy metals from water, especially tap water.
Among others, it can be suitably used as an adsorbent for water purifiers that remove lead from tap water.
〔ゼオライトを含む重金属吸着剤からのアルミニウムの溶出を抑制する方法〕
化合物Ａは、ゼオライトからのアルミニウムの溶出を抑制する。したがって、吸着剤に関する発明は、化合物Ａを用いることを特徴とする、ゼオライト含有重金属吸着剤からのアルミニウムの溶出を抑制する方法としても把握できる。
化合物Ａやゼオライトの説明は、吸着剤に関して述べた内容が適用される。
[Method for Suppressing Elution of Aluminum from Heavy Metal Adsorbent Containing Zeolite]
Compound A suppresses elution of aluminum from zeolite. Therefore, the invention relating to adsorbents can also be grasped as a method of suppressing the elution of aluminum from a zeolite-containing heavy metal adsorbent, which is characterized by using compound A.
The description of the compound A and zeolite applies to the content described with respect to the adsorbent.
以下、実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
〔化合物Ａ〕
以下の化合物１～１０を使用した。
前述した測定方法に従い、各化合物のＢＥＴ比表面積及びｐＨを測定した。
測定値を表１～２に示す。
[Compound A]
Compounds 1-10 below were used.
The BET specific surface area and pH of each compound were measured according to the measurement method described above.
The measured values are shown in Tables 1-2.
〔化合物１〕
硫酸チタニル（８０ｇ）を水（５００ｍｌ）に溶解して水溶液を得た。９０℃下で攪拌している前記水溶液へ、水酸化ナトリウム（濃度：２５％）を滴下してｐＨを３．５に調整し、沈殿物を得た。沈殿物を熟成（９０℃で１８時間）した後、固液分離、水洗、乾燥（１００℃で２４時間）及び粉砕に供して、メタチタン酸である化合物１を得た。
[Compound 1]
An aqueous solution was obtained by dissolving titanyl sulfate (80 g) in water (500 ml). Sodium hydroxide (concentration: 25%) was added dropwise to the aqueous solution stirred at 90° C. to adjust the pH to 3.5 to obtain a precipitate. After aging the precipitate (90° C. for 18 hours), it was subjected to solid-liquid separation, water washing, drying (100° C. for 24 hours) and pulverization to obtain compound 1 which is metatitanic acid.
〔化合物２〕
水酸化ナトリウムの滴下によりｐＨを７．０とした以外は化合物１と同様の方法にて、オルトチタン酸である化合物２を得た。
[Compound 2]
Compound 2, which is orthotitanic acid, was obtained in the same manner as for compound 1, except that sodium hydroxide was added dropwise to adjust the pH to 7.0.
〔化合物２ｂ〕
ｐＨを１１．０とした以外は、化合物２の調製と同様に操作を行い、ＢＥＴ比表面積が９ｍ2／ｇのオルトチタン酸である化合物２ｂを得た。
[Compound 2b]
Compound 2b, which is orthotitanic acid with a BET specific surface area of 9 m 2 /g, was obtained in the same manner as in the preparation of compound 2, except that the pH was changed to 11.0.
〔化合物３〕
第一稀元素工業(株)より販売されている「Ｒ水酸化ジルコニウム」を化合物３（水酸化ジルコニウム）とした。
[Compound 3]
"R zirconium hydroxide" sold by Daiichi Kigenso Kogyo Co., Ltd. was used as compound 3 (zirconium hydroxide).
〔化合物４〕
富士シリシア化学(株)より販売されている「サイリシア３５０」を、化合物４（含水酸化ケイ素）とした。
[Compound 4]
"Sylysia 350" sold by Fuji Silysia Chemical Co., Ltd. was used as compound 4 (hydrous silicon oxide).
〔化合物５〕
硝酸セリウム六水和物（１０ｇ）を水（５００ｍｌ）に溶解し、次いでセリウムと等モル量の過酸化水素水を添加して攪拌した後、更にアンモニア水を添加してｐＨを１０に調整し、沈殿物を得た。沈殿物を熟成（室温で６時間）した後、固液分離、水洗、乾燥（１００℃で２４時間）及び粉砕に供して、含水酸化セリウムである化合物５を得た。
[Compound 5]
Cerium nitrate hexahydrate (10 g) was dissolved in water (500 ml), then hydrogen peroxide solution in an amount equimolar to cerium was added, and the mixture was stirred. , to obtain a precipitate. After aging the precipitate (at room temperature for 6 hours), it was subjected to solid-liquid separation, washing with water, drying (at 100° C. for 24 hours) and pulverization to obtain Compound 5, which is hydrous cerium oxide.
〔化合物６〕
硫酸チタニル（１９ｇ）及びオキシ塩化ジルコニウム八水和物（３２ｇ）を水（５００ｍｌ）に溶解して水溶液を得た。室温下で攪拌している前記水溶液へ、２Ｍ濃度の水酸化ナトリウムを滴下してｐＨを１１に調整し、沈殿物を得た。沈殿物を熟成（室温で１８時間）した後、固液分離、水洗、乾燥（１００℃で２４時間）及び粉砕に供して、チタン・ジルコニウム複合含水酸化物である化合物６を得た。
[Compound 6]
Titanyl sulfate (19 g) and zirconium oxychloride octahydrate (32 g) were dissolved in water (500 ml) to give an aqueous solution. To the aqueous solution being stirred at room temperature, 2M sodium hydroxide was added dropwise to adjust the pH to 11 to obtain a precipitate. After aging the precipitate (at room temperature for 18 hours), it was subjected to solid-liquid separation, washing with water, drying (at 100° C. for 24 hours) and pulverization to obtain Compound 6, which is a titanium/zirconium composite hydrous oxide.
〔化合物７〕
塩化ランタン七水和物（２７ｇ）を水（５００ｍｌ）に溶解して水溶液を得た。室温下で攪拌している前記水溶液へ、アンモニア水（濃度：５％）を滴下してｐＨを１０に調整し、沈殿物を得た。沈殿物を熟成（室温で２４時間）した後、固液分離、水洗、乾燥（１００℃で２４時間）及び粉砕に供して、含水酸化ランタンである化合物７を得た。
[Compound 7]
An aqueous solution was obtained by dissolving lanthanum chloride heptahydrate (27 g) in water (500 ml). Aqueous ammonia (concentration: 5%) was added dropwise to the aqueous solution being stirred at room temperature to adjust the pH to 10 to obtain a precipitate. After aging the precipitate (at room temperature for 24 hours), it was subjected to solid-liquid separation, washing with water, drying (at 100° C. for 24 hours) and pulverization to obtain compound 7, which is hydrous lanthanum oxide.
〔化合物８〕
キシダ化学(株)より販売されている特級試薬の酸化チタンを化合物８とした。
化合物８はチタンの含水酸化物及び水酸化物に該当しないので、比較例で使用した。
[Compound 8]
Compound 8 was titanium oxide, which is a special grade reagent sold by Kishida Chemical Co., Ltd.
Compound 8 was used in Comparative Examples because it does not correspond to hydrous oxides and hydroxides of titanium.
〔化合物９〕
キシダ化学(株)より販売されている特級試薬の酸化ランタンを化合物９とした。
化合物９はランタンの含水酸化物及び水酸化物に該当しないので、比較例で使用した。
[Compound 9]
Lanthanum oxide, a special grade reagent sold by Kishida Chemical Co., Ltd., was used as compound 9.
Since compound 9 does not correspond to hydrous oxides and hydroxides of lanthanum, it was used in comparative examples.
〔化合物１０〕
キシダ化学(株)より販売されている特級試薬の水酸化マグネシウムを化合物１０（組成式：Ｍｇ（ＯＨ）2）とした。
化合物１０は、Ｓｉ、Ｔｉ、Ｚｒ、Ｃｅ及びＬａのいずれも含んでいないので、比較例で使用した。
[Compound 10]
Magnesium hydroxide, a special grade reagent sold by Kishida Chemical Co., Ltd., was used as compound 10 (compositional formula: Mg(OH) 2 ).
Compound 10 contains none of Si, Ti, Zr, Ce and La and was used in the comparative example.
〔化合物１１〕
キシダ化学(株)より販売されている特級試薬の水酸化ストロンチウムを化合物１１とした。
化合物１１は、Ｓｉ、Ｔｉ、Ｚｒ、Ｃｅ及びＬａのいずれも含んでいないので、比較例で使用した。
[Compound 11]
Strontium hydroxide, a special grade reagent sold by Kishida Chemical Co., Ltd., was used as compound 11.
Compound 11 contains none of Si, Ti, Zr, Ce and La and was used in the comparative example.
〔ゼオライト〕
シナネンゼオミック社製のＸ型ゼオライト、Ａ型ゼオライト、Ｙ型ゼオライト及びＰ型ゼオライト（製品名：ゼオミック。いずれも合成ゼオライト）を用いた。
ゼオライトのメジアン径は、レーザー回折・散乱式粒度分布測定法に従い測定した。
＜測定条件＞
測定装置：マイクロトラック・ベル(株) ＭＴ３３００ＥＸII
基準：体積基準
溶媒：水
粒子屈折率：１．３９
超音波処理：１２０秒（４０Ｗ）
各ゼオライトのメジアン径を表１（Ｘ型）及び表２（Ａ型、Ｐ型及びＹ型）に示す。
[Zeolite]
X-type zeolite, A-type zeolite, Y-type zeolite and P-type zeolite manufactured by Sinanen Zeomic Co., Ltd. (product name: Zeomic, all of which are synthetic zeolites) were used.
The median diameter of zeolite was measured according to a laser diffraction/scattering particle size distribution measurement method.
<Measurement conditions>
Measuring device: MT3300EXII manufactured by Microtrac Bell Co., Ltd.
Standard: volume standard solvent: water particle refractive index: 1.39
Sonication: 120 seconds (40W)
The median diameter of each zeolite is shown in Table 1 (X-type) and Table 2 (A-type, P-type and Y-type).
〔吸着剤の製造〕
吸着剤における化合物Ａの含量（質量％）が表１～２に記載された値となるように、所定質量のゼオライトと化合物Ａとをロッキングミキサーで乾式混合して、吸着剤を調製した。
表１～２中、化合物Ａの「含量（質量％）」は、化合物Ａとゼオライトとの合計質量に対する化合物Ａの含量（質量％）を示す。
[Production of adsorbent]
An adsorbent was prepared by dry-mixing a predetermined mass of zeolite and compound A in a rocking mixer such that the content (% by mass) of compound A in the adsorbent was the value shown in Tables 1 and 2.
In Tables 1 and 2, "content (% by mass)" of compound A indicates the content (% by mass) of compound A with respect to the total mass of compound A and zeolite.
〔吸着剤の評価〕
〔アルミニウムの溶出量〕
前述した測定法に従い、吸着剤からの「アルミニウムの溶出量」を測定した。
結果を表１～２に示す。
[Evaluation of adsorbent]
[Elution amount of aluminum]
The "amount of aluminum eluted" from the adsorbent was measured according to the measurement method described above.
The results are shown in Tables 1-2.
〔鉛の吸着〕
水道水からの鉛の除去率を指標にして重金属の吸着能を評価した。
比較例３並びに実施例３及び７の吸着剤の「鉛除去率」を以下の手順に従い測定した。
ＰＰ製容器に、吸着剤を５０ｍｇ秤量し、そこに１００００ｐｐｂの鉛イオンを含む模擬水道水５００ｍｌを添加し、プロペラ攪拌機を用いて２４時間、攪拌（回転数：１５０ｒｐｍ）した。
２４時間後、メンブランフィルター（孔径：０．４５μｍ）を用いて固液分離を行い、分離した液体中の鉛イオン濃度を原子吸光光度計で測定した。下記の計算式に従い鉛除去率を求めた。
鉛除去率（％）＝（（ａ－ｂ）／ａ）×１００（％）
ａ：吸着剤添加前の鉛イオン濃度（１００００ｐｐｂ）
ｂ：吸着剤を添加し２４時間攪拌した後の鉛イオン濃度
結果を表３に示す。
[Adsorption of lead]
The removal rate of lead from tap water was used as an index to evaluate the adsorption ability of heavy metals.
The "lead removal rate" of the adsorbents of Comparative Example 3 and Examples 3 and 7 was measured according to the following procedure.
50 mg of adsorbent was weighed into a PP container, 500 ml of simulated tap water containing 10000 ppb of lead ions was added, and the mixture was stirred for 24 hours using a propeller stirrer (rotation speed: 150 rpm).
After 24 hours, solid-liquid separation was performed using a membrane filter (pore size: 0.45 μm), and the lead ion concentration in the separated liquid was measured with an atomic absorption photometer. The lead removal rate was obtained according to the following formula.
Lead removal rate (%) = ((ab)/a) x 100 (%)
a: Lead ion concentration before addition of adsorbent (10000 ppb)
b: Lead ion concentration after adding adsorbent and stirring for 24 hours
Table 3 shows the results.
本発明は、重金属の除去が求められる技術分野、特に浄水器分野で利用可能である。 INDUSTRIAL APPLICABILITY The present invention can be used in technical fields requiring removal of heavy metals, particularly in the field of water purifiers.
Claims (11)
Ｓｉ、Ｔｉ、Ｚｒ、Ｃｅ又はＬａの含水酸化物又は水酸化物である化合物Ａを前記吸着剤へ添加する工程を含む方法。 A method for suppressing elution of aluminum from a heavy metal adsorbent containing zeolite, comprising:
A method comprising adding Compound A, which is a hydrous oxide or hydroxide of Si, Ti, Zr, Ce or La, to said adsorbent.
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